CN101168527A - Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof - Google Patents
Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof Download PDFInfo
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Abstract
The invention relates to the synthesis and the usage of the novel hindered amine light stabilizer undecylenic to pentadecanedioic acid (2, 2, 6, 6-tetramethyl piperidino) diester. The invention utilizes undecylenic acid, dodecanedioic acid, tridecanedioic acid, tetradecanoic acid and pentadecanedioic acid produced through microorganism fermentation paraffinic oil as the raw material, the undecylenic to pentadecanedioic acid diesters are synthesized firstly, then the ester exchange reaction is performed to produce the finished product, secondly, the catalytic agent adopts sodium methoxide, sodium ethoxide or sodium amide which has higher activity, is easy to prepare and segregate, and is suitable for the use in industry, the related reaction condition is bland, the technology is simple, and the invention is easy to realize industrialization. The invention has very good light protection performance, and the addition into lubricating oil hydrogenised base oil can obviously improve the light stability quality. The invention can replace the prior Tinuvin770 sebacic acid (2, 2, 6, 6-tetramethyl piperidino) diester product. The structure formula of the invention is shown in the following (I), wherein, n is equal to 11 or 12 or 13 or 14 or 15.
Description
Technical field
The present invention relates to a class hindered amine as light stabilizer compound, they are 11 or 12 or 13 or 14 or 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) esters, and the purposes of this class hindered amine light stabilizer.
Background technology
Hindered amine as light stabilizer (hindered amine light stabilizer is called for short HALS) is the novel photostabilizer of piperidine derivative class with space steric effect, and Japan develops first the seventies in 20th century.Hindered amine as light stabilizer has the ability of catching free radical, decompose hydroperoxide, and stabilising effect is higher 2～4 times than UV light absorber.Because it has unique, remarkable photo-protection performance, is subjected in the world generally paying attention to, and obtains extensive exploitation and application, becomes with fastest developing speed in the world, the fastest photostabilizer of rate of growth.General structure is:
R=H, substituted alkyl or substituted alkoxy
A=connects the auxiliary group of hindered piperidine base
Because it is many dissimilar that auxiliary group A and substituent group R have, and produced the piperidyl quantity polytype hindered amine as light stabilizer different with molecular weight thus.HALS is a kind of of radical scavenger, its Photostabilised performance has surpassed other any photostabilizer in the past, can be used as general efficiency light stablizers such as lubricating oil, plastics, synthon, coating, and thick, thin goods all there are good protection effect. be applied to plastic sheeting for farm use and have more unique advantages, it not only can prolong the work-ing life of plastic sheeting for farm use, and can see through the growth that long wave ultraviolet helps crop, therefore paid close attention to by people.
Parent molecule structure with HALS is divided, and is broadly divided into three classes: piperidines is that derivative, piperazine are that derivative, imidazolidone are derivative.And development research at present is more, market demand is bigger is piperidines system and piperazine system.The mechanism of action of HALS is very complicated, generally acknowledges that at present both at home and abroad HALS can reach the photo-protection effect by the synergy of catching free radical, hydroperoxide decomposition, catching heavy metal and this several aspects mechanism of quencher singlet oxygen.Sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester (Tinuvin-770) is low-molecular-weight typical products in numerous hindered amine light stabilizers.Come out the seventies,, be widely used in polyolefine material such as polypropylene and coating resin etc., can prevent from the gloss forfeiture to increase the service life, use very extensive because its cost is low and good light stability.
With with solvent treatment-solvent dewaxing-compare from the lubricant base of native process for refining production, hydrocracked lube base oil (abbreviation hydrogenated base oil) its have the viscosity index height, carbon residue is low, nitrogenous, sulfur-bearing is low, thermostability, low-temperature fluidity, lubricating oil additive is experienced characteristics such as good, and has an ability that good control greasy filth forms, be further to improve modern lubricating oil specification class, especially modulate high-grade I. C. engine oil and the high-quality technical oils provides primary condition.But hydrogenated base oil itself exists the defective of light stability difference, thereby has limited its application.Be exactly particularly when aerobic exists, be subjected to sun exposure or ultraviolet radiation occur after for some time darkening, muddy and then generate precipitation, have a strong impact on the mediation of the use properties of lubricating oil, follow-up oil product and dispatching from the factory of base oil.Selecting suitable photostabilizer is a kind of efficient ways of improving the hydrogenated base oil light stability.It is reported, the synthetic transformer oil of hydrogenated base oil with countries such as Iran, Saudi Arabia passes through to add suitable photostabilizer, not influencing surface tension, keeping dissolution in low temperature preferably under the situation, light stability has been reached and the suitable level of solvent treatment transformer oil product
Long-chain biatomic acid is to utilize the high carbon number normal paraffin of microbial fermentation and the meta-bolites that obtains, this product and derivative thereof are important source material or the intermediates of making cold-resistant plasticizer, quality lubricant, nylon fiber, engineering plastics, resin, coating, agricultural chemicals, medicine and spices etc., are a kind of very important fine chemical products.Because the long-chain biatomic acid occurring in nature does not exist, so can only adopt artificial synthesis to produce, its industrial process has two kinds, i.e. organic synthesis method and microbe fermentation method.And industrial value more greatly, more rising long-chain biatomic acid production method is microbe fermentation method.Long-chain biatomic acid is mainly based on chemical synthesis before the eighties in 20th century, the production process complexity, and production cost is higher, and its application is restricted.The beginning of the nineties, China utilized the Production by Microorganism Fermentation long-chain biatomic acid, greatly reduced cost, had improved output.Microbe fermentation method synthetic raw material mainly is the liquid wax in the oil, and along with the popularization of microbe fermentation method, it is reasonable that the long-chain biatomic acid price is tending towards.
Summary of the invention
The object of the invention is, utilizing 11 carbon dicarboxylic acids, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids or 15 carbon dicarboxylic acids of (commercially available) industrial paraffin oil Production by Microorganism Fermentation respectively is raw material, at first synthetic 11 to 15 carbon dicarboxylic acid diester, carry out transesterification reaction again and generate final product, the catalyzer of transesterification reaction is selected for use active higher and be easy to prepare and separates and sodium methylate or the sodium ethylate or the sodium amide of suitable industrial use, the reaction conditions gentleness that relates to, technology is simple, is easy to realize industrialization.The present invention has good photo-protection performance, and alternative currently available products Tinuvin770 sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester as general efficiency light stablizers such as lubricating oil, plastics, synthon or coating, obviously improves light stability.
11 to 15 carbon dicarboxylic acids two of the present invention (2,2,6, the 6-tetramethyl-piperidyl) ester, shown in the structural formula (I):
N=11 or 12 or 13 or 14 or 15 wherein.
The preparation method of described 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester follows these steps to carry out:
The preparation of a, 11 to 15 carbon dicarboxylic acid dimethyl esters or 11 to 15 carbon dicarboxylic acid diethyl esters:
11 carbon dicarboxylic acids that utilize (commercially available) paraffin oil microbial fermentation to produce, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids or 15 carbon dicarboxylic acids are raw material, add methyl alcohol or the ethanol and the catalyzer vitriol oil, behind the reaction 4-5h, the sherwood oil that adds 2～4 times of pure volumes, separate the sherwood oil upper materials and the lower floor's material that contain 11 to 15 carbon dicarboxylic acid diester, with lower floor's material esterification 4-5h that refluxes again, last combining extraction liquid and reaction solution, NaOH solution washing with 2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets 11 to 15 carbon dicarboxylic acid dimethyl esters or 11 to 15 carbon dicarboxylic acid diethyl esters;
The preparation of b, 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
With step a 11 to 15 carbon dicarboxylic acid diester and 2,2,6, the pure and mild solvent anhydrous dimethyl of 6-tetramethyl piperidine benzene adds in the reactor, be heated to 70-80 ℃, treat that it is that reaction solution is that equal phase time adds catalyzer sodium methylate or sodium ethylate or sodium amide that piperidines alcohol is dissolved in dimethylbenzene fully, back flow reaction 8-10h, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and the adding boiling point is 60-90 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated, the ethanolic soln recrystallization with 65% gets white crystal.
Described 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester is as the preparation hindered amine as light stabilizer, is used for the anti-oxidant of polypropylene, high density polyethylene(HDPE), urethane, polystyrene and ABS resin or as the particularly lubricant base produced of hydrocracking process anti-oxidant of preparation lubricating oil.
The preparation method of concrete 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester carries out as follows:
At first 11 or 12 or 13 or 14 or 15 carbon dicarboxylic acid diester is synthetic: be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add 11 to 15 carbon dicarboxylic acids, the methyl alcohol (or ethanol) and the catalyzer vitriol oil, behind reaction 4～5h, add the sherwood oil that is equivalent to 2～4 times of pure volumes to reaction solution, tell upper materials that contains 11 to 15 carbon dicarboxylic acid diester and sherwood oil and the lower floor's material that contains 11 to 15 carbon dicarboxylic acids, with lower floor's material esterification 4-5h that once refluxes again, final reaction liquid and extraction liquid merge, behind 2% NaOH solution washing, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly get 11 to 15 carbon dicarboxylic acid diester, its acid number≤0.2mgKOH/g.
Next 11 or 12 or 13 or 14 or 15 carbon dicarboxylic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester is synthetic: thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add 11 or 12 or 13 or 14 or 15 carbon dicarboxylic acid diester, 2,2,6, the pure and mild solvent anhydrous dimethyl of 6-tetramethyl piperidine benzene, be heated to 70-80 ℃, treat that it is that reaction solution is that equal phase time adds catalyzer sodium methylate or sodium ethylate or sodium amide, back flow reaction 8-10h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and the adding boiling point is 60-90 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, the ethanolic soln recrystallization with 65% gets white crystal.
Described 11 to 15 carbon dicarboxylic acids are to be obtained by biological fermentation 11 to pentadecane hydrocarbon.
11 to 15 carbon dicarboxylic acids two (2 of the present invention, 2,6, the 6-tetramethyl-piperidyl) ester, as the alternative existing sebacic acid two (2 of novel hindered amine light stabilizer, 2,6,6-tetramethyl-piperidyl) ester (Tinuvin770) is as photostabilizer, be applicable to polypropylene, high density polyethylene(HDPE), urethane, polystyrene, ABS resin, in the middle of the lubricant base that also can be applicable to produce through hydrocracking process, compare with Tinuvin770, wherein odd number 11,13 and 15 carbon dicarboxylic acids two (2,2,6,6-tetramethyl-piperidyl) the ester fusing point has reduced about 40 ℃, and the application in the middle of hydrogenated base oil has more superiority like this.And the auxiliary group of hindered amine as light stabilizer is a straight-chain paraffin among the present invention, and itself is exactly the primary structure of a lot of top-grade lubricating oils, such hindered amine as light stabilizer of more suitable use.
Description of drawings
Referring to accompanying drawing
Fig. 1 be the present invention's 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester as photostabilizer and reference substance sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester performance evaluation map in the lube oil hydrogenation base oil, wherein
+ lube oil hydrogenation base oil blank;
△ is in the same old way, sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester;
◆ 11 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester;
■ SL-AH two (2,2,6, the 6-tetramethyl-piperidyl) ester;
▲ tridecanyldicarboxylic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester;
● ten four-carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester;
15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester.
Embodiment
Below in conjunction with specific embodiment the present invention is further described:
Embodiment 1:
The preparation of 11 carbon dicarboxylic acid dimethyl esters:
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add 11 carbon dicarboxylic acid 0.1mol, methyl alcohol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 4h, add the sherwood oil that is equivalent to 2 times of quantity of methyl alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid dimethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets 11 carbon dicarboxylic acid dimethyl esters of weak yellow liquid shape;
The preparation of 11 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add 11 carbon dicarboxylic acid dimethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 70 ℃, treat that it is that reaction solution is that equal phase time adds the sodium methoxide catalyst that is equivalent to 11 carbon dicarboxylic acid dimethyl ester quality 0.8%, back flow reaction 9h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 60 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 42-44 ℃, and yield is 98.1%.
Embodiment 2:
The preparation of 11 carbon dicarboxylic acid diethyl esters:
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add 11 carbon dicarboxylic acid 0.1mol, ethanol 50ml and catalyzer vitriol oil 0.4ml, behind the reaction 5h, add the sherwood oil that is equivalent to 2 times of amount of alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid diethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification 4h at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets 11 carbon dicarboxylic acid diethyl esters of weak yellow liquid shape.
The preparation of 11 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add 11 carbon dicarboxylic acid diethyl ester 0.1mol, 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 80 ℃, treat that it is that reaction solution is that equal phase time adds the sodium ethylate catalyzer that is equivalent to 11 carbon dicarboxylic acid diethyl ester quality 0.8%, back flow reaction 10h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 90 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 42-44 ℃, and yield is 96.5%.
Embodiment 3
The preparation of SL-AH dimethyl ester
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add SL-AH 0.1mol, methyl alcohol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 4.5h, add the sherwood oil that is equivalent to 4 times of quantity of methyl alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid dimethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets the SL-AH dimethyl ester of weak yellow liquid shape;
The preparation of SL-AH two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add SL-AH dimethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 75 ℃, treat that it is that reaction solution is that equal phase time adds the sodium amide catalyzer that is equivalent to SL-AH dimethyl ester quality 0.8%, back flow reaction 10h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 70 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 81-83 ℃, and yield is 98.5%.
Embodiment 4
The preparation of SL-AH diethyl ester
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add SL-AH 0.1mol, ethanol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 4.5h, add the sherwood oil that is equivalent to 2 times of amount of alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid diethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets the SL-AH diethyl ester of weak yellow liquid shape;
The preparation of SL-AH two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add SL-AH diethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 75 ℃, treat that it is that reaction solution is that equal phase time adds the sodium amide catalyzer that is equivalent to SL-AH diethyl ester quality 0.8%, back flow reaction 10h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 70 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 81-83 ℃, and yield is 97.1%.
Embodiment 5
The preparation of tridecanyldicarboxylic acid methyl esters
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add tridecanyldicarboxylic acid 0.1mol, methyl alcohol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 5h, add the sherwood oil that is equivalent to 3 times of quantity of methyl alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid dimethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets the tridecanyldicarboxylic acid dimethyl ester of weak yellow liquid shape;
The preparation of tridecanyldicarboxylic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add tridecanyldicarboxylic acid dimethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 78 ℃, treat that it is that reaction solution is that equal phase time adds the sodium methoxide catalyst that is equivalent to tridecanyldicarboxylic acid dimethyl ester quality 0.8%, back flow reaction 8.5h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 80 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 34-35 ℃, and yield is 97.7%.
Embodiment 6
The preparation of tridecanyldicarboxylic acid ethyl ester
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add tridecanyldicarboxylic acid 0.1mol, ethanol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 5h, add the sherwood oil that is equivalent to 2 times of amount of alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid diethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets the tridecanyldicarboxylic acid diethyl ester of weak yellow liquid shape;
The preparation of tridecanyldicarboxylic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add tridecanyldicarboxylic acid diethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 72 ℃, treat that it is that reaction solution is that equal phase time adds the sodium methoxide catalyst that is equivalent to tridecanyldicarboxylic acid diethyl ester quality 0.8%, back flow reaction 8.5h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 80 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 34-35 ℃, and yield is 95.8%.
Embodiment 7
The preparation of ten four-carbon dicarboxylic acid methyl esters
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add ten four-carbon dicarboxylic acid 0.1mol, methyl alcohol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 4h, add the sherwood oil that is equivalent to 2 times of quantity of methyl alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid dimethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets ten four-carbon dicarboxylic acid dimethyl esters of weak yellow liquid shape;
The preparation of ten four-carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add ten four-carbon dicarboxylic acid dimethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 80 ℃, treat that it is that reaction solution is that equal phase time adds the sodium ethylate catalyzer that is equivalent to ten four-carbon dicarboxylic acid dimethyl ester quality 0.8%, back flow reaction 9h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 90 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 79-80 ℃, and yield is 95.2%.
Embodiment 8
The preparation of ten four-carbon dicarboxylic acid ethyl esters
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add tridecanyldicarboxylic acid 0.1mol, ethanol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 5h, add the sherwood oil that is equivalent to 2 times of amount of alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid diethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets ten four-carbon dicarboxylic acid diethyl esters of weak yellow liquid shape;
The preparation of ten four-carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add ten four-carbon dicarboxylic acid diethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 72 ℃, treat that it is that reaction solution is that equal phase time adds the sodium ethylate catalyzer that is equivalent to tridecanyldicarboxylic acid diethyl ester quality 0.8%, back flow reaction 9h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 90 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 79-80 ℃, and yield is 95.9%.
Embodiment 9
The preparation of 15 carbon dicarboxylic acid methyl esters
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add 15 carbon dicarboxylic acid 0.1mol, methyl alcohol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 4h, add the sherwood oil that is equivalent to 2 times of quantity of methyl alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid dimethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets 15 carbon dicarboxylic acid dimethyl esters of weak yellow liquid shape;
The preparation of 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add 15 carbon dicarboxylic acid dimethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 78 ℃, treat that it is that reaction solution is that equal phase time adds the sodium amide catalyzer that is equivalent to 15 carbon dicarboxylic acid dimethyl ester quality 0.8%, back flow reaction 9.5h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 75 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 43-44 ℃, and yield is 98.3%.
The preparation of 15 carbon dicarboxylic acid ethyl esters
Be equipped with magnetic stirring apparatus, thermometer, in the three-necked flask of reflux condensing tube, add 15 carbon dicarboxylic acid 0.1mol, ethanol 40ml and catalyzer vitriol oil 0.3ml, behind the reaction 5h, add the sherwood oil that is equivalent to 2 times of amount of alcohol to reaction solution, tell upper materials that contains long-chain biatomic acid diethyl ester and sherwood oil and the lower floor's material that contains long-chain biatomic acid, esterification at last again refluxes lower floor's material, merge reaction solution and extraction liquid, NaOH solution washing with 50ml2%, extremely neutral with deionized water wash again, underpressure distillation steams solvent, promptly gets 15 carbon dicarboxylic acid diethyl esters of weak yellow liquid shape;
The preparation of 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester:
Thermometer and the apparatus,Soxhlet's that 4 molecular sieves are housed are installed on reactor, add 15 carbon dicarboxylic acid diethyl ester 0.1mol and 2,2,6,6-tetramethylpiperidinol 0.4mol and 25ml anhydrous dimethyl benzene, be heated to 70 ℃, treat that it is that reaction solution is that equal phase time adds the sodium amide catalyzer that is equivalent to 15 carbon dicarboxylic acid diethyl ester quality 0.8%, back flow reaction 9.5h that piperidines alcohol is dissolved in dimethylbenzene fully, with TLC detection reaction terminal point, reaction is cooled to 80 ℃ after finishing, and adding 40ml boiling point is 75 ℃ sherwood oil dilution, be washed to neutral back solvent evaporated and get product, ethanolic soln recrystallization with 65% gets white needle-like crystals, and fusing point is 43-44 ℃, and yield is 97.3%.
Embodiment 11
11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester is as the purposes of light stability.
11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester and reference substance sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester are joined in the lube oil hydrogenation base oil, and add-on is 0.5% of a hydrogenated base oil quality.Blank base oil sample and specimen contain in thickness respectively to be in the ultraviolet spectrophotometer cuvette of 1cm, to be positioned in the shaking culture case that 50 ℃ of constant temperature vibrate, and use UV-irradiation, every the 2-3h taking-up, at 501nm wavelength place measurement transmittance.Its result as shown in drawings, the result shows relatively excellent performance of 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) the ester light stability that the present invention relates to and sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester (Tinuvin770).
Claims (3)
1. one kind 11 to 15 carbon dicarboxylic acids two (2,2,6, the 6-tetramethyl-piperidyl) ester hindered amine as light stabilizer, it is characterized in that structural formula is shown in (I):
N=11 or 12 or 13 or 14 or 15 wherein.
2. 11 to 15 carbon dicarboxylic acids two (2 according to claim 1,2,6,6 one tetramethyl-piperidyls) ester, it is characterized in that utilizing 11 carbon dicarboxylic acids of paraffin oil microbial fermentation production, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids or 15 carbon dicarboxylic acids are raw material, by preparing 11 to 15 carbon dicarboxylic acid dimethyl esters or 11 to 15 carbon dicarboxylic acid diethyl esters through catalytic esterification with methyl alcohol or ethanol, again in the anhydrous dimethyl benzene solvent, with sodium methylate or sodium ethylate or sodium amide is catalyzer, with 2,2,6, the 6-tetramethylpiperidinol prepares by transesterification reaction.
3. 11 to 15 carbon dicarboxylic acids two according to claim 1 (2,2,6, the 6-tetramethyl-piperidyl) ester is used for the oxidation resistant purposes of lubricating oil, plastics, synthon or coating as hindered amine as light stabilizer.
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| CNA200710180031XA CN101168527A (en) | 2007-11-16 | 2007-11-16 | Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845013A (en) * | 2010-05-18 | 2010-09-29 | 北京天罡助剂有限责任公司 | Multi-hindered piperidyl-containing hindered amide compound used for light stabilizer and preparation method thereof |
| CN101381477B (en) * | 2008-10-15 | 2011-04-27 | 天津大学 | Hindered amine light stabilizer and synthetic method thereof |
| CN102382039A (en) * | 2011-08-08 | 2012-03-21 | 宿迁联盛化学有限公司 | Synthesizing technology of hindered amine light stabilizer Tinuvin-770 |
| CN104403763A (en) * | 2014-10-17 | 2015-03-11 | 无锡中石油润滑脂有限责任公司 | Photo-stabilization type lubricating grease and preparation method thereof |
| CN110387064A (en) * | 2019-07-12 | 2019-10-29 | 西安工业大学 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
| CN116463160A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Ashless antioxidant additive, application thereof and composite lubricant |
| CN116463159A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Antioxidant additive, preparation method and application thereof |
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- 2007-11-16 CN CNA200710180031XA patent/CN101168527A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381477B (en) * | 2008-10-15 | 2011-04-27 | 天津大学 | Hindered amine light stabilizer and synthetic method thereof |
| CN101845013A (en) * | 2010-05-18 | 2010-09-29 | 北京天罡助剂有限责任公司 | Multi-hindered piperidyl-containing hindered amide compound used for light stabilizer and preparation method thereof |
| CN102382039A (en) * | 2011-08-08 | 2012-03-21 | 宿迁联盛化学有限公司 | Synthesizing technology of hindered amine light stabilizer Tinuvin-770 |
| CN104403763A (en) * | 2014-10-17 | 2015-03-11 | 无锡中石油润滑脂有限责任公司 | Photo-stabilization type lubricating grease and preparation method thereof |
| CN110387064A (en) * | 2019-07-12 | 2019-10-29 | 西安工业大学 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
| CN116463160A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Ashless antioxidant additive, application thereof and composite lubricant |
| CN116463159A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Antioxidant additive, preparation method and application thereof |
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